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WO2002018365A1 - N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents - Google Patents

N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents Download PDF

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Publication number
WO2002018365A1
WO2002018365A1 PCT/EP2001/002840 EP0102840W WO0218365A1 WO 2002018365 A1 WO2002018365 A1 WO 2002018365A1 EP 0102840 W EP0102840 W EP 0102840W WO 0218365 A1 WO0218365 A1 WO 0218365A1
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Prior art keywords
amino
benzene
diamino
group
methyl
Prior art date
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Ceased
Application number
PCT/EP2001/002840
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German (de)
French (fr)
Inventor
Laurent Chassot
Hans-Jürgen BRAUN
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Procter and Gamble Deutschland GmbH
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Wella GmbH
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Publication date
Priority to BR0107155-6A priority Critical patent/BR0107155A/en
Priority to EP01925442A priority patent/EP1313724B1/en
Priority to AU2001252194A priority patent/AU2001252194B2/en
Priority to DE50102156T priority patent/DE50102156D1/en
Priority to AU5219401A priority patent/AU5219401A/en
Priority to US10/111,464 priority patent/US6849097B2/en
Application filed by Wella GmbH filed Critical Wella GmbH
Priority to CA002435328A priority patent/CA2435328C/en
Priority to AT01925442T priority patent/ATE265446T1/en
Priority to JP2002523483A priority patent/JP2004507532A/en
Publication of WO2002018365A1 publication Critical patent/WO2002018365A1/en
Anticipated expiration legal-status Critical
Priority to US10/922,443 priority patent/US6887281B2/en
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/415—Aminophenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/418—Amines containing nitro groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D233/24—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms

Definitions

  • the invention relates to new N-heteroarylmethyl-p-phenylenediamine derivatives and agents containing these compounds for the oxidative dyeing of keratin fibers.
  • Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring.
  • the coloration arises from the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent.
  • 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 1,4-diaminobenzene are used as developer substances, while resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol and derivatives of m- Phenylenediamines are to be mentioned.
  • Oxidation dyes which are used to dye human hair, are subject to numerous additional requirements in addition to dyeing in the desired intensity.
  • the dyes have to be harmless from a toxicological and dermatological point of view and the hair colorations obtained have good lightfastness, permanent wave fastness, acid fastness and rubbing fastness.
  • such stains must remain stable over a period of at least 4 to 6 weeks without exposure to light, friction and chemical agents. It is also necessary that by combining more suitable Developer substances and coupler substances can produce a wide range of different color shades.
  • the present invention therefore relates to N-heteroarylmethyl-p-phenylenediamine derivatives of the general formula (I) or their physiologically tolerable, water-soluble salts,
  • X1 is sulfur, nitrogen, C-R6 or N-R5;
  • X2 is sulfur, nitrogen, C-R6 or N-R5
  • X3 is sulfur, nitrogen, oxygen, C-R6 or
  • R1 is hydrogen, a -CC 4 alkyl group or
  • R2, R3 may be the same or different and, independently of one another, are hydrogen or a C-I-C ⁇ alkyl group
  • R4, R6 can be the same or different and, independently of one another, are the same as hydrogen, a halogen atom, a cyano group, a CrC 4 alkoxy group, a Ci-C ⁇ alkyl group, a C 1 -C 4 alkyl thioether group, a mercapto group, a nitro group, an amino group, , a C ⁇ -C 4 alkylamino group, a di alkylamino (C ⁇ -C 4) a di (C ⁇ -C4 hydroxy- alkyl) amino group, a C ⁇ -C 4 hydroxyalkyl-amino group, a trifluoromethane group, a - C (O) CH 3 - group, a -C (O) CF 3 group, a -Si (CH 3 ) 3 - group, a -C-hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl group;
  • R5 is hydrogen, a Ci-C ⁇ -alkyl group, one
  • Preferred compounds of the formula (I) are those in which (i) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen or (ii) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X1 is the same Is sulfur or NH and X2 is nitrogen or C-R6 and X3 is C-R6 or (iii) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X3 is sulfur or oxygen and X1 and X2 is C-R6 or (iv) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X2 is sulfur or oxygen and X1 and X3 are C-R6.
  • N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) which are particularly suitable for the purposes of the overall invention are N-thiophene-3-ylmethyl-1,4-diamino-benzene, N-furan-3-ylmethyl-1,4-diamino -benzene, N- (1 H-imidazol-2-ylmethyl) -1, 4-diamino-benzene, N- (1 H-pyrrol-2-ylmethyl) -1, 4-diamino-benzene and N-thiophene-2 -ylmethyl-1, 4-diamino-benzene or their physiologically tolerable salts.
  • the compounds of the formula (I) can be used both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
  • inorganic or organic acids such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
  • N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) can be prepared using known synthetic processes.
  • the synthesis of the compounds of formula (I) can be carried out, for example, as follows: (1) By reductive alkylation of a substituted benzene of the formula (II)
  • Rb has the meaning NHRa or NO 2 ,
  • Ra represents a protective group, as for example in the chapter
  • the compounds of the formula (I) enable a wide range of different shades, ranging from blonde to brown, purple, violet to blue and black shades, and are outstandingly suitable for use in colorants for keratin fibers.
  • the present invention therefore furthermore relates to compositions for the oxidative dyeing of keratin fibers, such as, for example, hair, furs, feathers or wool, and in particular human hair, based on a developer substance-coupler substance combination which, as developer substance, comprises at least one N-heteroarylmethyl Contain p-phenylene diamine derivative of the formula (I) described above.
  • the N-heteroarylmethyl-p-phenylenediamine derivative of the formula (I) is preferably used in the colorant according to the invention in an amount of about 0.005 to 20 percent by weight, an amount of about 0.01 to 5.0 percent by weight and in particular 0.1 up to 2.5 percent by weight is particularly preferred.
  • Preferred coupler substances are 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino -1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1- (2-hydroxyethoxy) -5-methyl-benzene, 2,4 -Di [(2-hydroxyethyl) amino] -1,5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino-6-methoxy-2- (methylamino) -pyridine, 2,6 -Diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1, 3-diamino-benzene, 2,4-dia
  • the advantageous properties of the p-diaminobenzene derivatives of the formula (I) described here suggest that they be used as the sole developer substance, it is of course also possible to use the p-diaminobenzene derivatives of the formula (I) together with known developer substances, such as for example 1,4-diaminobenzene, 2,5-diamino-toluene, 2,5-diaminophenylethyl alcohol, 4-aminophenol and its Derivatives, for example 4-amino-3-methylphenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole or tetraaminopyrimidines, can be used.
  • developer substances such as for example 1,4-diaminobenzene, 2,5-diamino-toluene, 2,5-diaminophenylethyl alcohol, 4-aminophenol and its Derivatives, for example 4-amino-3-methylphenol,
  • the coupler substances and developer substances can each be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5.0 percent by weight and in particular 0.1 to 2.5 percent by weight.
  • the total amount of developer-coupler combination contained in the colorant described here is preferably about 0.01 to 20 percent by weight, with an amount of about 0.02 to 10 percent by weight and in particular 0.2 to 6 percent by weight being particularly preferred.
  • the developer substances and coupler substances are generally used in approximately equimolar amounts; however, it is not disadvantageous if the developer substances are present in this respect in a certain excess or deficit (for example in a ratio (coupler: developer) of 1: 2 to 1: 0.5).
  • the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, and also conventional direct dyes, for example triphenylmethane dyes such as 4 - [(4'-aminophenyl) - (4'- imino-2 ", 5" - cyclohexadien-1 "-ylidene) -methyl] -2-methylaminobenzene-monohydrochloride (Cl 42 510) and 4 - [(4 , -amino-3 , -methyl-phenyl) - (4" -imino-3 "-methyl-2", 5 "- cyclohexadien-1” -ylidene) -methyl] -2-methyl-aminobenzene monohydrochloride (Cl 42 520), aromatic nitro dyes such as 4- (2'-hydroxyethyl) amino-nitrotoluene, 2-amino-4,6-dinitrophenol,
  • the coupler substances and developer substances as well as the other color components can also be in the form of the physiologically compatible salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of the salts
  • organic or inorganic acids such as hydrochloric acid or sulfuric acid
  • Bases for example as alkali phenolates, are used.
  • the colorants may also contain other customary cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, and also perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care agents.
  • the preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution.
  • the particularly preferred preparation forms are a cream, a gel or an emulsion.
  • Your Composition represents a mixture of the dye components with the additives customary for such preparations.
  • Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerol or glycols such as 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides and oxyethylated fatty acid ester, also thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, and
  • ingredients mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 weight percent.
  • the colorant according to the invention can react weakly acidic, neutral or alkaline.
  • it has a pH of 6.5 to 11.5, the basic setting preferably being carried out with ammonia.
  • organic amines for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide can also be used.
  • inorganic bases such as sodium hydroxide and potassium hydroxide can also be used.
  • the colorant described above is mixed with an oxidizing agent immediately before use and an amount sufficient for the hair dyeing treatment, depending on the fullness of the hair, generally about 60 to 200 grams, of this mixture is applied to the hair.
  • the main oxidizing agents used to develop hair color are hydrogen peroxide or its addition compounds to urea, melamine, sodium borate or sodium carbonate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all at higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time.
  • the mixture is allowed to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, this rinse is washed with a shampoo and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.
  • the colorants according to the invention with a content of diaminobenzene derivatives of the formula (I) as developer substance enable colorations with excellent color fastness, especially in terms of light fastness, wash fastness and rub fastness.
  • the colorants according to the invention offer a wide range of different color nuances, depending on the type and composition of the color components, which ranges from blonde to brown, purple, violet to blue and black shades. The shades are characterized by their special color intensity.
  • the very good dyeing properties of the colorants according to the present application are further shown in the fact that these agents in particular also enable graying, chemically not previously damaged hair to be colored easily and with good coverage.
  • N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) used in the composition according to the invention are readily soluble in water and enable dyeings with high color intensity and excellent color fastness, in particular with regard to light fastness, wash fastness and rub fastness. They also have excellent storage stability, particularly as a component of the colorants described above.
  • Examples 1 Synthesis of N-HeteroarylmethvI-p-phenylenediamines 0.031 g (0.15 mmol) of tert-butyl N- (4-aminophenyl) carbamate and 0.1 mmol of the corresponding aldehyde are dissolved in 1,2-dichloroethane. Then 0.1 ml of an acetic acid solution (1 molar in 1, 2-dichloroethane) and 0.06 g of NaBH (OAc) 3 (0.3 mmol) are added and the reaction mixture is stirred for 5 to 15 hours at room temperature.
  • OAc NaBH
  • the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate.
  • the solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether / ethyl acetate (9: 1).
  • the product thus obtained is heated to 50 ° C. in 4 ml of ethanol and 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution.
  • the precipitate is filtered off, washed twice with 1 ml of ethanol and then dried. a.
  • Examples 2 Synthesis of N1-heteroarylmethyl-2-methyl-1,4-diaminobenzenes and N4-heteroarylmethyl-2-methyl-1,4-diaminobenzenes 0.033 g (0.15 mmol) of a mixture of N- (4-amino-2- methyl-phenyl) -carbamic acid tert-butyl ester and N- (4-amino-3-methyl-phenyl) -carbamic acid tert-butyl ester and 0.10 mmol of the corresponding aldehyde are dissolved in 1, 2-dichloroethane.
  • the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate.
  • the solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether / ethyl acetate (9: 1).
  • the product obtained in this way is heated to 50 ° C. in 4 ml of ethanol and 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution.
  • the precipitate is filtered off, washed twice with 1 ml of ethanol and then dried. a.
  • Cream-like color carrier compositions of the following composition are produced:

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Abstract

The invention relates to N-heteroarylmethyl-p-phenylendiamine derivatives of general formula (I) or the physiologically compatible water soluble salts thereof (I), in addition to oxidation hair colouring agents based on a combination of developing/coupling substances which contain at least one N-Heteroaryl-methyl-p-phenylendiamine derivative of formula (I).

Description

B e s c h r e i b u n g Description

N-Heteroarylmethyl-p-phenylendiamin-Derivate sowie diese Verbindungen enthaltende OxidationsfärbemittelN-heteroarylmethyl-p-phenylenediamine derivatives and oxidation colorants containing these compounds

Die Erfindung betrifft neue N-Heteroarylmethyl-p-phenylendiamin-Derivate sowie diese Verbindungen enthaltende Mittel zum oxidativen Färben von Keratinfasem.The invention relates to new N-heteroarylmethyl-p-phenylenediamine derivatives and agents containing these compounds for the oxidative dyeing of keratin fibers.

Auf dem Gebiet der Färbung von Keratinfasem, insbesondere der Haarfärbung, haben Oxidationsfarbstoffe eine wesentliche Bedeutung erlangt. Die Färbung entsteht hierbei durch Reaktion bestimmter Entwicklersubstanzen mit bestimmten Kupplersubstanzen in Gegenwart eines geeigneten Oxidationsmittels. Als Entwicklersubstanzen werden hierbei insbesondere 2,5-Diaminotoluol, 2,5-Diaminophenylethylalkohol, p-Aminophenol und 1 ,4-Diaminobenzol eingesetzt, während als Kupplersubstanzen beispielsweise Resorcin, 4-Chlorresorcin, 1-Naphthol, 3-Aminophenol und Derivate des m-Phenylendiamins zu nennen sind. An Oxidationsfarbstoffe, die zur Färbung menschlicher Haare verwendet werden, werden neben der Färbung in der gewünschten Intensität zahlreiche zusätzliche Anforderungen gestellt. So müssen die Farbstoffe in toxikologischer und dermatologischer Hinsicht unbedenklich sein und die erzielten Haarfärbungen eine gute Lichtechtheit, Dauerwellechtheit, Säureechtheit und Reibeechtheit aufweisen. Auf jeden Fall aber müssen solche Färbungen ohne Einwirkung von Licht, Reibung und chemischen Mitteln über einen Zeitraum von mindestens 4 bis 6 Wochen stabil bleiben. Außerdem ist es erforderlich, daß durch Kombination geeigneter Entwicklersubstanzen und Kupplersubstanzen eine breite Palette verschiedener Farbnuancen erzeugt werden kann.Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The coloration arises from the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. In particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 1,4-diaminobenzene are used as developer substances, while resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol and derivatives of m- Phenylenediamines are to be mentioned. Oxidation dyes, which are used to dye human hair, are subject to numerous additional requirements in addition to dyeing in the desired intensity. For example, the dyes have to be harmless from a toxicological and dermatological point of view and the hair colorations obtained have good lightfastness, permanent wave fastness, acid fastness and rubbing fastness. In any case, such stains must remain stable over a period of at least 4 to 6 weeks without exposure to light, friction and chemical agents. It is also necessary that by combining more suitable Developer substances and coupler substances can produce a wide range of different color shades.

In der US 5 540 738 werden Oxidationshaarfärbemittel beschrieben, welche u.a. N-Furfuryl-p-phenylendiamin sowie ein Jodid enthalten. Diese Färbemittel sind jedoch nicht in jeder Hinsicht befriedigend, insbesondere kann ohne den Zusatz von Jodid kein befriedigendes Färbeergebnis erzielt werden.In US 5 540 738 oxidation hair colorants are described, which among other things. Contain N-furfuryl-p-phenylenediamine and an iodide. However, these coloring agents are not satisfactory in all respects, in particular a satisfactory coloring result cannot be achieved without the addition of iodide.

Es bestand daher weiterhin ein dringendes Bedürfnis für neue Farbstoffvorstufen für Oxidationsfärbemittel, welche auch ohne den Zusatz von Jodid intensive Färbungen von Keratinfasem ermöglichen.There was therefore still an urgent need for new dye precursors for oxidation colorants, which enable intensive coloring of keratin fibers even without the addition of iodide.

Es wurde nun gefunden, dass intensivere braune, blaue und rote Farbnuancen erhalten werden, wenn man N-Heteroarylmethyl-p- phenylendiamin-Derivate gemäß der allgemeinen Formel (I) zusammen mit üblichen Kupplerverbindungen zur Kupplung bringt.It has now been found that more intense brown, blue and red shades are obtained if N-heteroarylmethyl-p-phenylenediamine derivatives according to the general formula (I) are coupled together with conventional coupler compounds.

Gegenstand der vorliegende Erfindung sind daher N-Heteroarylmethyl-p- phenylendiamin-Derivate der allgemeinen Formel (I) oder deren physiologisch verträgliche, wasserlösliche Salze,The present invention therefore relates to N-heteroarylmethyl-p-phenylenediamine derivatives of the general formula (I) or their physiologically tolerable, water-soluble salts,

Figure imgf000003_0001
X1 gleich Schwefel, Stickstoff, C-R6 oder N-R5 ist;
Figure imgf000003_0001
X1 is sulfur, nitrogen, C-R6 or N-R5;

X2 gleich Schwefel, Stickstoff, C-R6 oder N-R5 istX2 is sulfur, nitrogen, C-R6 or N-R5

X3 gleich Schwefel, Stickstoff, Sauerstoff, C-R6 oderX3 is sulfur, nitrogen, oxygen, C-R6 or

N-R5 ist;Is N-R5;

R1 gleich Wasserstoff, einer Cι-C4-Alkylgruppe oder einerR1 is hydrogen, a -CC 4 alkyl group or

Cι-C4-Hydroxyalkylgruppe ist ;Is -C 4 hydroxyalkyl group;

R2,R3 gleich oder verschieden sein können und unabhängig voneinander gleich Wasserstoff oder einer C-I-CΘ- Alkylgruppe sind;R2, R3 may be the same or different and, independently of one another, are hydrogen or a C-I-CΘ alkyl group;

R4,R6 gleich oder verschieden sein können und unabhängig voneinander gleich Wasserstoff, einem Halogenatom, einer Cyanogruppe, einer CrC4-Alkoxygruppe, einer Ci-Cβ-Alkylgruppe, einer Cι-C4-Alkylthioethergruppe, einer Mercaptogruppe, einer Nitrogruppe, einer Aminogruppe, einer Cι-C4-Alkylaminogruppe, einer Di(Cι-C4)-alkylaminogruppe, einer Di(Cι-C4-hydroxy- alkyl)aminogruppe, einer Cι-C4-Hydroxyalkyl-amino- gruppe, einer Trifluormethangruppe, einer -C(O)CH3- Gruppe, einer -C(O)CF3-Gruppe, einer -Si(CH3)3- Gruppe, einer Cι-C -Hydroxyalkylgruppe oder einer C3-C4 Dihydroxyalkylgruppe sind;R4, R6 can be the same or different and, independently of one another, are the same as hydrogen, a halogen atom, a cyano group, a CrC 4 alkoxy group, a Ci-Cβ alkyl group, a C 1 -C 4 alkyl thioether group, a mercapto group, a nitro group, an amino group, , a Cι-C 4 alkylamino group, a di alkylamino (Cι-C 4) a di (Cι-C4 hydroxy- alkyl) amino group, a Cι-C 4 hydroxyalkyl-amino group, a trifluoromethane group, a - C (O) CH 3 - group, a -C (O) CF 3 group, a -Si (CH 3 ) 3 - group, a -C-hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl group;

R5 gleich Wasserstoff, einer Ci-Cβ-Alkylgruppe, einerR5 is hydrogen, a Ci-Cβ-alkyl group, one

Cι-C4-Hydroxyalkylgruppe, einer Phenylgruppe oder einer Acetylgruppe ist; wobei mindestens einer und maximal zwei der Reste X1 bis X3 gleichC 1 -C 4 hydroxyalkyl group, a phenyl group or an acetyl group; where at least one and a maximum of two of the radicals X1 to X3 are the same

C-R6 sind und maximal einer der Reste X1 bis X3 gleich Schwefel,C-R6 and a maximum of one of the radicals X1 to X3 are sulfur,

Sauerstoff oder N-R5 ist. Als erfindungsgemäß geeigneteVerbindungen der Formel (I) können beispielweise genannt werden:Is oxygen or N-R5. Compounds of the formula (I) which are suitable according to the invention can be mentioned, for example:

N-Thiophen-3-ylmethyl-1 ,4-diamino-benzol, N-Furan-3-ylmethyl-1 ,4- diamino-benzol, N-(1 H-lmidazol-2-ylmethyl)-1 ,4-diamino-benzol, N-(1 H-Pyrol-2-ylmethyl)-1 ,4-diamino-benzol, N-(N-Methyl-pyrol-2- ylmethyl)-1 ,4-diamino-benzol, N-Thiophen-2-ylmethyl-1 ,4-diamino-benzol, N-Thiazol-2-ylmethyl-1 ,4-diamino-benzol, N-(5-Nitro-thiophen-2-ylmethyl)- 1 ,4-diamino-benzol, N-(3-Methyl-thiophen-2-ylmethyl)-1 ,4-diamino-benzol, N-(2-Methyl-thiophen-3-ylmethyl)-1 ,4-diamino-benzol, N-(4-Methyl- thiophen-3-ylmethyl)-1 ,4-diamino-benzol, N-(5-Methyl-thiophen-2- ylmethyl)-1 ,4-diamino-benzol, N-(3-Chlor-thiophen-2-ylmethyl)-1 ,4- diamino-benzol, N-(4-Methyl-thiophen-2-ylmethyl)-1 ,4-diamino-benzol, N-(4-Chlor-thiophen-2-ylmethyl)-1 ,4-diamino-benzol, N-(5-Methyl- thiophen-2-ylmethyl)-1 ,4-diamino-benzol, N-(5-Chlor-thiophen-2-ylmethyl)- 1 ,4-diamino-benzol, 2-[(4-Amino-phenyl)-thiophen-2-ylmethyl-amino]- ethanol, 2-[(4-Amino-phenyl)- 1 H-Imidazol -2-ylmethyl-amino]-ethanol, N-Methyl-N-thiophen-3-ylmethyl-1 ,4-diamino-benzol, N-Methyl-N-furan-3- ylmethyl-1 ,4-diamino-benzol, N-Methyl-N-(1 H-imidazol-2-ylmethyl)-1 ,4- diamino-benzol, N1-(1H-lmidazol-2-ylmethyl)-1 ,4-diamino-2-methyl- benzol, N4-(1 H-lmidazol-2-ylmethyl)-1 ,4-diamino-2-methyl-benzol, N1-Furan-3-ylrr.ethyl-1 ,4-diamino-2-methyl-benzol, N4-Furan-3-ylmethyl- 1 ,4-diamino-2-methyl-benzol, N 1 -Thiophen-2-ylmethyl-1 ,4-diamino-2- methyl-benzol, N4-thiophen-2-ylmethyl-1 ,4-diamino-2-methyl- benzol, 2-{5-Amino-2-[(furan-2-ylmethyl)-amino]-phenyl}-ethanol, 2-{6-Amino-3- [(furan-2-ylmethyI)-amino]-phenyl}-ethanol, 2-{5-Amino-2-[(thiophen-3- ylmethyl)-amino]-phenyl}-ethanol, 2-{6-Amino-3-[(thiophen-3-ylmethyl)- amino]-phenyl}-ethanol . 2-{5-Amino-2-[(thiophen-2-ylmethyl)- amino]-phenyl}-ethanol, 2-{6-Amino-3-[(thiophen-2-ylmethyl)-amino]- phenylj-ethanol; Bevorzugt sind Verbindungen der Formel (I) in denen (i) R1, R2 und R3 oder R1, R2, R3 und R4 Wasserstoff bedeuten oder (ii) R1, R2 und R3 oder R1, R2, R3 und R4 Wasserstoff bedeuten und X1 gleich Schwefel oder N-H ist und X2 gleich Stickstoff oder C-R6 ist und X3 gleich C-R6 ist oder (iii) R1, R2 und R3 oder R1, R2, R3 und R4 gleich Wasserstoff sind und X3 gleich Schwefel oder Sauerstoff ist und X1 und X2 gleich C-R6 sind oder (iv) R1, R2 und R3 oder R1, R2, R3 und R4 gleich Wasserstoff sind und X2 gleich Schwefel oder Sauerstoff ist und X1 und X3 gleich C-R6 sind.N-thiophene-3-ylmethyl-1,4-diamino-benzene, N-furan-3-ylmethyl-1,4-diamino-benzene, N- (1 H-imidazol-2-ylmethyl) -1,4-diamino -benzene, N- (1 H-pyrol-2-ylmethyl) -1, 4-diamino-benzene, N- (N-methyl-pyrol-2-ylmethyl) -1, 4-diamino-benzene, N-thiophene- 2-ylmethyl-1,4-diamino-benzene, N-thiazol-2-ylmethyl-1,4-diamino-benzene, N- (5-nitro-thiophene-2-ylmethyl) -1,4-diamino-benzene, N- (3-methylthiophene-2-ylmethyl) -1, 4-diamino-benzene, N- (2-methyl-thiophene-3-ylmethyl) -1, 4-diamino-benzene, N- (4-methyl - thiophene-3-ylmethyl) -1, 4-diamino-benzene, N- (5-methyl-thiophene-2-ylmethyl) -1, 4-diamino-benzene, N- (3-chloro-thiophene-2-ylmethyl) ) -1, 4- diamino-benzene, N- (4-methyl-thiophene-2-ylmethyl) -1, 4-diamino-benzene, N- (4-chloro-thiophene-2-ylmethyl) -1, 4- diamino-benzene, N- (5-methyl-thiophene-2-ylmethyl) -1, 4-diamino-benzene, N- (5-chloro-thiophene-2-ylmethyl) - 1, 4-diamino-benzene, 2- [(4-aminophenyl) thiophene-2-ylmethylamino] ethanol, 2 - [(4-aminophenyl) -1 H -imidazole -2-ylmethylamino] ethanol, N-methyl-N thiophene-3-y lmethyl-1,4-diamino-benzene, N-methyl-N-furan-3-ylmethyl-1,4-diamino-benzene, N-methyl-N- (1 H -imidazol-2-ylmethyl) -1,4 - diamino-benzene, N1- (1H-imidazol-2-ylmethyl) -1, 4-diamino-2-methyl-benzene, N4- (1 H-imidazol-2-ylmethyl) -1, 4-diamino-2- methyl-benzene, N1-furan-3-ylrr.ethyl-1, 4-diamino-2-methyl-benzene, N4-furan-3-ylmethyl-1, 4-diamino-2-methyl-benzene, N 1 -thiophene -2-ylmethyl-1, 4-diamino-2-methyl-benzene, N4-thiophene-2-ylmethyl-1, 4-diamino-2-methyl-benzene, 2- {5-amino-2 - [(furan- 2-ylmethyl) amino] phenyl} ethanol, 2- {6-amino-3- [(furan-2-ylmethyl) amino] phenyl} ethanol, 2- {5-amino-2 - [( thiophene-3-ylmethyl) amino] phenyl} ethanol, 2- {6-amino-3 - [(thiophene-3-ylmethyl) amino] phenyl} ethanol. 2- {5-Amino-2 - [(thiophene-2-ylmethyl) amino] phenyl} ethanol, 2- {6-amino-3 - [(thiophene-2-ylmethyl) amino] phenylj-ethanol ; Preferred compounds of the formula (I) are those in which (i) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen or (ii) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X1 is the same Is sulfur or NH and X2 is nitrogen or C-R6 and X3 is C-R6 or (iii) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X3 is sulfur or oxygen and X1 and X2 is C-R6 or (iv) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X2 is sulfur or oxygen and X1 and X3 are C-R6.

Im Sinne der Gesamterfindung besonders geeignete N-Heteroarylmethyl- p-phenylendiamin-Derivate der Formel (I) sind N-Thiophen-3-ylmethyl-1 ,4- diamino-benzol, N-Furan-3-ylmethyl-1 ,4-diamino-benzol, N-(1 H-Imidazol- 2-ylmethyl)-1 ,4-diamino-benzol, N-(1 H-Pyrrol-2-ylmethyl)-1 ,4-diamino- benzol und N-Thiophen-2-ylmethyl-1 ,4-diamino-benzol oder deren physiologisch verträgliche Salze.N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) which are particularly suitable for the purposes of the overall invention are N-thiophene-3-ylmethyl-1,4-diamino-benzene, N-furan-3-ylmethyl-1,4-diamino -benzene, N- (1 H-imidazol-2-ylmethyl) -1, 4-diamino-benzene, N- (1 H-pyrrol-2-ylmethyl) -1, 4-diamino-benzene and N-thiophene-2 -ylmethyl-1, 4-diamino-benzene or their physiologically tolerable salts.

Die Verbindungen der Formel (I) können sowohl als freie Basen als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, wie zum Beispiel Salzsäure, Schwefelsäure, Phosphorsäure, Essigsäure, Propionsäure, Milchsäure oder Zitronensäure, eingesetzt werden.The compounds of the formula (I) can be used both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

Die Herstellung der erfindungsgemäßen N-Heteroarylmethyl-p- phenylendiamin-Derivate der Formel (I) kann unter Verwendung von bekannten Syntheseverfahren erfolgen. Die Synthese der Verbindungen der Formel (I) kann beispielsweise wie folgt durchgeführt werden: (1) Durch eine reduktive Alkylierung eines substituierten Benzols der Formel (II)The N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) can be prepared using known synthetic processes. The synthesis of the compounds of formula (I) can be carried out, for example, as follows: (1) By reductive alkylation of a substituted benzene of the formula (II)

Figure imgf000007_0001
Figure imgf000007_0001

mit einer Heteroarylverbindung der Formel (III)with a heteroaryl compound of the formula (III)

Figure imgf000007_0002
Figure imgf000007_0002

worinwherein

Rb die Bedeutung NHRa oder NO2 hat,Rb has the meaning NHRa or NO 2 ,

Ra eine Schutzgruppe darstellt, wie sie zum Beispiel in dem KapitelRa represents a protective group, as for example in the chapter

„Protective Groups" in Organic Synthesis, Kapitel 7, Wiley Interscience,"Protective Groups" in Organic Synthesis, Chapter 7, Wiley Interscience,

1991 beschrieben wird,1991 is described

X1, X2, X3, R1, R2, R3 und R4 die in Formel (I) gennante Bedeutung haben, undX1, X2, X3, R1, R2, R3 and R4 have the meaning given in formula (I), and

(2) Abspaltung der Schutzgruppe oder Abspaltung der Schutzgruppe und(2) deprotection or deprotection and

Reduktion der Nitrogruppe.Reduction of the nitro group.

Die Verbindungen der Formel (I) ermöglichen eine breite Palette verschiedener Farbtöne, die sich von blonden über braune, purpurne, violette bis hin zu blauen und schwarzen Farbtönen erstreckt und eignen sich hervorragend für die Verwendung in Färbemitteln für Keratinfasem. Ein weiterer Gegenstand der vorliegenden Erfindung sind daher Mittel zum oxidativen Färben von Keratinfasem, wie zum Beispiel Haaren, Pelzen, Federn oder Wolle, und insbesondere menschlichen Haaren, auf der Basis einer Entwicklersubstanz-Kupplersubstanz-Kombination, welche als Entwicklersubstanz mindestens ein N-Heteroarylmethyl-p-phenylen- diamin-Derivat der vorstehend beschriebenen Formel (I) enthalten.The compounds of the formula (I) enable a wide range of different shades, ranging from blonde to brown, purple, violet to blue and black shades, and are outstandingly suitable for use in colorants for keratin fibers. The present invention therefore furthermore relates to compositions for the oxidative dyeing of keratin fibers, such as, for example, hair, furs, feathers or wool, and in particular human hair, based on a developer substance-coupler substance combination which, as developer substance, comprises at least one N-heteroarylmethyl Contain p-phenylene diamine derivative of the formula (I) described above.

Das N-Heteroarylmethyl-p-phenylendiamin-Derivat der Formel (I) wird in dem erfindungsgemäßen Färbemittel vorzugsweise in einer Menge von etwa 0,005 bis 20 Gewichtsprozent verwendet, wobei eine Einsatzmenge von etwa 0,01 bis 5,0 Gewichtsprozent und insbesondere 0,1 bis 2,5 Gewichtsprozent besonders bevorzugt ist.The N-heteroarylmethyl-p-phenylenediamine derivative of the formula (I) is preferably used in the colorant according to the invention in an amount of about 0.005 to 20 percent by weight, an amount of about 0.01 to 5.0 percent by weight and in particular 0.1 up to 2.5 percent by weight is particularly preferred.

Als Kupplersubstanzen kommen vorzugsweise 2,6-Diamino-pyridin, 2-Amino-4-[(2-hydroxyethyl)amino]-anisol, 2,4-Diamino-1-fluor-5-methyl- benzol, 2,4-Diamino-1-methoxy-5-methyl-benzol, 2,4-Diamino-1-ethoxy-5- methyl-benzol, 2,4-Diamino-1-(2-hydroxyethoxy)-5-methyl-benzol, 2,4-Di[(2-hydroxyethyl)amino]-1 ,5-dimethoxy-benzol, 2,3-Diamino-6- methoxy-pyridin, 3-Amino-6-methoxy-2-(methylamino)-pyridin, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino-2,6-dimethoxy-pyridin, 1 ,3-Diamino-benzol, 2,4-Diamino-1-(2-hydroxyethoxy)-benzol, 2,4-Diamino-1 ,5-di(2-hydroxyethoxy)-benzol, 1-(2-Aminoethoxy)-2,4- diamino-benzol, 2-Amino-1-(2-hydroxyethoxy)-4-methylamino-benzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxyethyl)amino]-anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1 -ethoxy-benzol, 5-Methyl-2-(1 - methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Amino- ethyl)amino]-ani!in, 1 ,3-Di(2,4-diaminophenoxy)-propan, Di(2,4-diamino- phenoxy)-methan, 1 ,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2-hydroxy- ethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethyl- amino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl- phenol, 5-Amino-4-methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl- phenol, 3-Amino-2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino- 2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-2- methyl-phenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-Methoxyethyl)- aminoj-phenol, 5-Amino-2-ethyl-phenol, 2-(4-Amino-2-hydroxyphenoxy)- ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxy- propyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-2-methyl- phenol, 2-Amino-3-hydroxy-pyridin, 5-Amino-4-chlor-2-methyl-phenol, 1-Naphthol, 1 ,5-Dihydroxy-naphthalin, 1 ,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol- acetat, 1 ,3-Dihydroxy-benzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1 ,3- dihydroxy-benzol, 1 ,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1 ,5-Dichlor- 2,4-dihydroxy-benzol, 1 ,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy- phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1 ,3-benzo- dioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino- benzoesäure, 3,4-Dihydro-6-hydroxy-1 ,4(2H)-benzoxazin, 6-Amino-3,4- dihydro-1 ,4(2H)-benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy- indol, 7-Hydroxy-indol und 2,3-lndolindion in Betracht.Preferred coupler substances are 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino -1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1- (2-hydroxyethoxy) -5-methyl-benzene, 2,4 -Di [(2-hydroxyethyl) amino] -1,5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino-6-methoxy-2- (methylamino) -pyridine, 2,6 -Diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1, 3-diamino-benzene, 2,4-diamino-1- (2-hydroxyethoxy) benzene, 2 , 4-diamino-1,5-di (2-hydroxyethoxy) benzene, 1- (2-aminoethoxy) -2,4-diamino-benzene, 2-amino-1- (2-hydroxyethoxy) -4-methylamino- benzene, 2,4-diaminophenoxyacetic acid, 3- [di (2-hydroxyethyl) amino] aniline, 4-amino-2-di [(2-hydroxyethyl) amino] -1-ethoxy-benzene, 5-methyl- 2- (1-methylethyl) phenol, 3 - [(2-hydroxyethyl) amino] aniline, 3 - [(2-aminoethyl) amino] -ani! In, 1, 3-di (2,4- diaminophenoxy) propane, di (2,4-diamino-phenoxy) methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bi s (2-hydroxyethyl) aminotoluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethyl aminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy- 2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6- methyl-phenol, 3-amino-phenol, 2 - [(3-hydroxyphenyl) amino] -acetamide, 5 - [(2-hydroxyethyl) amino] -2-methyl-phenol, 3 - [(2-hydroxyethyl) amino] -phenol, 3 - [(2-methoxyethyl) aminoj-phenol, 5-amino-2-ethylphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 3 - [(2,3-dihydroxypropyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3 -hydroxy-pyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1, 5-dihydroxy-naphthalene, 1, 7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2.7 -Dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1, 3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 2-chloro-1, 3-dihydroxy-benzene, 1, 2 -Dichlor-3,5-dihydroxy-4-methyl-benzene, 1, 5-dichloro-2,4-dihydroxy-benzene, 1 , 3-Dihydroxy-2-methyl-benzene, 3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline, 5 - [(2-hydroxyethyl) amino] -1, 3-benzo-dioxol, 6-bromo 1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1, 4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1 , 4 (2H) -benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7- Hydroxy-indole and 2,3-indolinedione.

Obwohl die vorteilhaften Eigenschaften der hier beschriebenen p-Diaminobenzol-Derivate der Formel (I) es nahelegen, diese als alleinige Entwicklersubstanz zu verwenden, ist es selbstverständlich auch möglich, die p-Diaminobenzol-Derivate der Formel (I) gemeinsam mit bekannten Entwicklersubstanzen, wie zum Beispiel 1 ,4-Diaminobenzol, 2,5-Diamino- toluol, 2,5-Diaminophenylethylalkohol, 4-Aminophenol und seinen Derivaten, beispielsweise 4-Amino-3-methylphenol, 4,5-Diamino-1-(2- hydroxyethyl)-pyrazol oder Tetraaminopyrimidinen, einzusetzen.Although the advantageous properties of the p-diaminobenzene derivatives of the formula (I) described here suggest that they be used as the sole developer substance, it is of course also possible to use the p-diaminobenzene derivatives of the formula (I) together with known developer substances, such as for example 1,4-diaminobenzene, 2,5-diamino-toluene, 2,5-diaminophenylethyl alcohol, 4-aminophenol and its Derivatives, for example 4-amino-3-methylphenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole or tetraaminopyrimidines, can be used.

Die Kupplersubstanzen und Entwicklersubstanzen können in dem erfindungsgemäßen Färbemittel jeweils einzeln oder im Gemisch miteinander enthalten sein, wobei die Gesamtmenge an Kupplersubstanzen und Entwicklersubstanzen in dem erfindungsgemäßen Färbemittel (bezogen auf die Gesamtmenge des Färbemittels) jeweils etwa 0,005 bis 20 Gewichtsprozent, vorzugsweise etwa 0,01 bis 5,0 Gewichtsprozent und insbesondere 0,1 bis 2,5 Gewichtsprozent, beträgt.The coupler substances and developer substances can each be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5.0 percent by weight and in particular 0.1 to 2.5 percent by weight.

Die Gesamtmenge der in dem hier beschriebenen Färbemittel enthaltenen Entwicklersubstanz-Kupplersubstanz-Kombination beträgt vorzugsweise etwa 0,01 bis 20 Gewichtsprozent, wobei eine Menge von etwa 0,02 bis 10 Gewichtsprozent und insbesondere 0,2 bis 6 Gewichtsprozent besonders bevorzugt ist. Die Entwicklersubstanzen und Kupplersubstanzen werden im allgemeinen in etwa äquimolaren Mengen eingesetzt; es ist jedoch nicht nachteilig, wenn die Entwicklersubstanzen diesbezüglich in einem gewissen Überschuß oder Unterschuß (beispielsweise in einem Verhältnis (Kuppler : Entwickler) von 1 :2 bis 1 :0,5) vorhanden sind.The total amount of developer-coupler combination contained in the colorant described here is preferably about 0.01 to 20 percent by weight, with an amount of about 0.02 to 10 percent by weight and in particular 0.2 to 6 percent by weight being particularly preferred. The developer substances and coupler substances are generally used in approximately equimolar amounts; however, it is not disadvantageous if the developer substances are present in this respect in a certain excess or deficit (for example in a ratio (coupler: developer) of 1: 2 to 1: 0.5).

Weiterhin kann das erfindungsgemäße Färbemittel zusätzlich andere Farbkomponenten, beispielsweise 6-Amino-2-methylphenol und 2-Amino- 5-methylphenol, sowie ferner übliche direktziehende Farbstoffe, zum Beispiel Triphenylmethanfarbstoffe wie 4-[(4'-aminophenyl)-(4'-imino-2",5"- cyclohexadien-1"-yliden)-methyl]-2-methylaminobenzol-monohydrochlorid (C.l. 42 510) und 4-[(4,-amino-3,-methyl-phenyl)-(4"-imino-3"-methyl-2",5"- cyclohexadien-1"-yliden)-methyl]-2-methyl-aminobenzol monohydrochlorid (C.l. 42 520), aromatische Nitrofarbstoffe wie 4-(2'-hydroxyethyl)amino- nitrotoluol, 2-Amino-4,6-dinitrophenol, 2-Amino-5-(2'-hydroxyethyl)amino- nitrobenzol, 2-Chlor-6-(ethylamino)-4-nitrophenol, 4-Chlor-N-(2- hydroxyethyl-2-nitroanilin, 5-Chlor-2-hydroxy-4-nitroanilin, 2-Amino-4- chlor-6-nitrophenol und 1-[(2'-Ureidoethyl)amino-4-nitrobenzol, Azofarbstoffe wie 6-[(4'-Aminophenyl)azo]-5-hydroxy-naphthalin-1 - sulfonsäure-Natriumsalz (C.l. 14 805) und Dispersionsfarbstoffe wie beispielsweise 1 ,4-Diaminoanthrachinon und 1 ,4,5,8-Tetraamino- antrachinon, enthalten. Die Färbemittel können diese Farbkomponenten in einer Menge von etwa 0,1 bis 4 Gewichtsprozent enthalten.Furthermore, the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, and also conventional direct dyes, for example triphenylmethane dyes such as 4 - [(4'-aminophenyl) - (4'- imino-2 ", 5" - cyclohexadien-1 "-ylidene) -methyl] -2-methylaminobenzene-monohydrochloride (Cl 42 510) and 4 - [(4 , -amino-3 , -methyl-phenyl) - (4" -imino-3 "-methyl-2", 5 "- cyclohexadien-1" -ylidene) -methyl] -2-methyl-aminobenzene monohydrochloride (Cl 42 520), aromatic nitro dyes such as 4- (2'-hydroxyethyl) amino-nitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene, 2-chlorine -6- (ethylamino) -4-nitrophenol, 4-chloro-N- (2-hydroxyethyl-2-nitroaniline, 5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and 1 - [(2'-ureidoethyl) amino-4-nitrobenzene, azo dyes such as 6 - [(4'-aminophenyl) azo] -5-hydroxy-naphthalene-1 - sulfonic acid sodium salt (Cl 14 805) and disperse dyes such as 1 , 4-diaminoanthraquinone and 1, 4,5,8-tetraaminoanthraquinone, The colorants can contain these color components in an amount of about 0.1 to 4 percent by weight.

Selbstverständlich können die Kupplersubstanzen und Entwicklersubstanzen sowie die anderen Farbkomponenten, sofern es Basen sind, auch in Form der physiologisch verträglichen Salze mit organischen oder anorganischen Säuren, wie beispielsweise Salzsäure oder Schwefelsäure, beziehungsweise - sofern sie aromatische OH-Gruppen besitzen - in Form der Salze mit Basen, zum Beispiel als Alkaliphenolate, eingesetzt werden.Of course, the coupler substances and developer substances as well as the other color components, if they are bases, can also be in the form of the physiologically compatible salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of the salts Bases, for example as alkali phenolates, are used.

Darüber hinaus können in den Färbemitteln, falls diese zur Färbung von Haaren verwendet werden sollen, noch weitere übliche kosmetische Zusätze, beispielsweise Antioxidantien wie Ascorbinsäure, Thioglykolsäure oder Natriumsulfit, sowie Parfümöle, Komplexbildner, Netzmittel, Emulgatoren, Verdicker und Pflegestoffe enthalten sein. Die Zubereitungsform des erfindungsgemäßen Färbemittels kann beispielsweise eine Lösung, insbesondere eine wäßrige oder wäßrigalkoholische Lösung sein. Die besonders bevorzugten Zubereitungsformen sind jedoch eine Creme, ein Gel oder eine Emulsion. Ihre Zusammensetzung stellt eine Mischung der Farbstoffkomponenten mit den für solche Zubereitungen üblichen Zusätzen dar.In addition, if the colorants are to be used for dyeing hair, the colorants may also contain other customary cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, and also perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care agents. The preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. However, the particularly preferred preparation forms are a cream, a gel or an emulsion. Your Composition represents a mixture of the dye components with the additives customary for such preparations.

Übliche Zusätze in Lösungen, Cremes, Emulsionen oder Gelen sind zum Beispiel Lösungsmittel wie Wasser, niedere aliphatische Alkohole, beispielsweise Ethanol, Propanol oder Isopropanol, Glycerin oder Glykole wie 1 ,2-Propylenglykol, weiterhin Netzmittel oder Emulgatoren aus den Klassen der anionischen, kationischen, amphoteren oder nichtionogenen oberflächenaktiven Substanzen wie zum Beispiel Fettalkoholsulfate, oxethylierte Fettalkoholsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Alkyltrimethylammoniumsalze, Alkylbetaine, oxethylierte Fettalkohole, oxethylierte Nonylphenole, Fettsäurealkanolamide und oxethylierte Fettsäureester ferner Verdicker wie höhere Fettalkohole, Stärke, Cellulosederivate, Petrolatum, Paraffinöl und Fettsäuren, sowie außerdem Pflegestoffe wie kationische Harze, Lanolinderivate, Cholesterin, Pantothensäure und Betain. Die erwähnten Bestandteile werden in den für solche Zwecke üblichen Mengen verwendet, zum Beispiel die Netzmittel und Emulgatoren in Konzentrationen von etwa 0,5 bis 30 Gewichtsprozent, die Verdicker in einer Menge von etwa 0,1 bis 25 Gewichtsprozent und die Pflegestoffe in einer Konzentration von etwa 0,1 bis 5,0 Gewichtsprozent.Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerol or glycols such as 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides and oxyethylated fatty acid ester, also thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, and also care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The ingredients mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 weight percent.

Je nach Zusammensetzung kann das erfindungsgemäße Färbemittel schwach sauer, neutral oder alkalisch reagieren. Insbesondere weist es einen pH-Wert von 6,5 bis 11 ,5 auf, wobei die basische Einstellung vorzugsweise mit Ammoniak erfolgt. Es können aber auch organische Amine, zum Beispiel Monoethanolamin und Triethanolamin, oder auch anorganische Basen wie Natriumhydroxid und Kaliumhydroxid Verwendung finden. Für eine pH-Einstellung im sauren Bereich kommen anorganische oder organische Säuren, zum Beispiel Phosphorsäure, Essigsäure Zitronensäure oder Weinsäure, in Betracht.Depending on the composition, the colorant according to the invention can react weakly acidic, neutral or alkaline. In particular, it has a pH of 6.5 to 11.5, the basic setting preferably being carried out with ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. Come for a pH adjustment in the acidic range inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid.

Für die Anwendung zur oxidativen Färbung von Haaren vermischt man das vorstehend beschriebene Färbemittel unmittelbar vor dem Gebrauch mit einem Oxidationsmittel und trägt eine für die Haarfärbebehandlung ausreichende Menge, je nach Haarfülle, im allgemeinen etwa 60 bis 200 Gramm, dieses Gemisches auf das Haar auf.For use in the oxidative dyeing of hair, the colorant described above is mixed with an oxidizing agent immediately before use and an amount sufficient for the hair dyeing treatment, depending on the fullness of the hair, generally about 60 to 200 grams, of this mixture is applied to the hair.

Als Oxidationsmittel zur Entwicklung der Haarfärbung kommen hauptsächlich Wasserstoffperoxid oder dessen Additionsverbindungen an Harnstoff, Melamin, Natriumborat oder Natriumcarbonat in Form einer 3- bis 12-prozentigen, vorzugsweise 6-prozentigen, wässrigen Lösung, aber auch Luftsauerstoff in Betracht. Wird eine 6-prozentige Wasserstoffperoxid-Lösung als Oxidationsmittel verwendet, so beträgt das Gewichtsverhältnis zwischen Haarfärbemittel und Oxidationsmittel 5:1 bis 1 :2, vorzugeweise jedoch 1 :1. Größere Mengen an Oxidationsmittel werden vor allem bei höheren Farbstoffkonzentrationen im Haarfärbemittel, oder wenn gleichzeitig eine stärkere Bleichung des Haares beabsichtigt ist, verwendet. Man läßt das Gemisch bei 15 bis 50 Grad Celsius etwa 10 bis 45 Minuten lang, vorzugsweise 30 Minuten lang, auf das Haar einwirken, spült sodann das Haar mit Wasser aus und trocknet es. Gegebenenfalls wird im Anschluß an diese Spülung mit einem Shampoo gewaschen und eventuell mit einer schwachen organischen Säure, wie zum Beispiel Zitronensäure oder Weinsäure, nachgespült. Anschließend wird das Haar getrocknet.The main oxidizing agents used to develop hair color are hydrogen peroxide or its addition compounds to urea, melamine, sodium borate or sodium carbonate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all at higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time. The mixture is allowed to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, this rinse is washed with a shampoo and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.

Die erfindungsgemäßen Färbemittel mit einem Gehalt an Diaminobenzol- Derivaten der Formel (I) als Entwicklersubstanz ermöglichen Färbungen mit ausgezeichneter Farbechtheit, insbesondere was die Lichtechtheit, Waschechtheit und Reibeechtheit anbetrifft. Hinsichtlich der färberischen Eigenschaften bieten die erfindungsgemäßen Färbemittel je nach Art und Zusammensetzung der Farbkomponenten eine breite Palette verschiedener Farbnuancen, welche sich von blonden über braune, purpurne, violette bis hin zu blauen und schwarzen Farbtönen erstreckt. Hierbei zeichnen sich die Farbtöne durch ihre besondere Farbintensität aus. Die sehr guten färberischen Eigenschaften der Färbemittel gemäß der vorliegenden Anmeldung zeigen sich weiterhin darin, daß diese Mittel insbesondere auch eine Anfärbung von ergrauten, chemisch nicht vorgeschädigten Haaren problemlos und mit guter Deckkraft ermöglichen.The colorants according to the invention with a content of diaminobenzene derivatives of the formula (I) as developer substance enable colorations with excellent color fastness, especially in terms of light fastness, wash fastness and rub fastness. With regard to the coloring properties, the colorants according to the invention offer a wide range of different color nuances, depending on the type and composition of the color components, which ranges from blonde to brown, purple, violet to blue and black shades. The shades are characterized by their special color intensity. The very good dyeing properties of the colorants according to the present application are further shown in the fact that these agents in particular also enable graying, chemically not previously damaged hair to be colored easily and with good coverage.

Die in dem erfindungsgemäßen Mittel verwendeten N-Heteroarylmethyl-p- phenylendiamin-Derivate der Formel (I) sind gut in Wasser löslich und ermöglichen Färbungen mit hoher Farbintensität und ausgezeichneter Farbechtheit, insbesondere was die Lichtechtheit, Waschechtheit und Reibeechtheit anbetrifft. Sie weisen weiterhin eine ausgezeichnete Lagerstabilität, insbesondere als Bestandteil der vorstehend beschriebenen Färbemittel, auf.The N-heteroarylmethyl-p-phenylenediamine derivatives of the formula (I) used in the composition according to the invention are readily soluble in water and enable dyeings with high color intensity and excellent color fastness, in particular with regard to light fastness, wash fastness and rub fastness. They also have excellent storage stability, particularly as a component of the colorants described above.

Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf zu beschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.

B e i s p i e l eB e i s p i e l e

Beispiele 1 : Synthese von N-HeteroarylmethvI-p-phenylendiaminen 0,031 g (0,15 mmol) N-(4-Aminophenyl)-carbaminsäure-tert-butylester und 0,1 mmol des entsprechenden Aldehyds werden in 1 ,2-Dichlorethan gelöst. Anschliessend werden 0,1 ml einer Essigsäurelösung (1 -molar in 1 ,2-Dichlorethan) und 0,06 g NaBH(OAc)3 (0,3 mmol) zugegeben und die Reaktionmischung wird 5 bis 15 Stunden bei Raumtemperatur gerührt. Nach Beendigung der Reaktion wird die Reaktionsmischung in 10 ml Essigsäureethylester gegossen, die organische Phase mit Natriumhydrogencarbonat extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/Essigsäureethylester (9:1) gereinigt. Das so erhaltene Produkt wird in 4 ml Ethanol und 1 ,5 ml einer 2,9 molaren ethanolische Salzsäurelösung auf 50 °C erwärmt. Der Niederschlag wird abfiltriert, zweimal mit 1 ml Ethanol gewaschen und sodann getrocknet. a. N-Thiophen-3-ylmethyl-1 -4-diamino-benzol Hvdrochlorid Verwendeter Aldehyd: Thiophen-3-carbaldehyd Ausbeute: 0,025g (90% der Theorie) Massenspketrum: MH+ 205(100) b. N-Furan-3-ylmethyl-1 ,4-diamino-benzol Hvdrochlorid Verwendeter Aldehyd: Furan-3-carbaldehyd Ausbeute: 0,025g (95% der Theorie) Massenspketrum: MH+ 189(100) c. N-(1 H-lmidazol-2-ylmethv0-1 ,4-diamino-benzol Hvdrochlorid Verwendeter Aldehyd: lmidazol-2-carbaldehydExamples 1: Synthesis of N-HeteroarylmethvI-p-phenylenediamines 0.031 g (0.15 mmol) of tert-butyl N- (4-aminophenyl) carbamate and 0.1 mmol of the corresponding aldehyde are dissolved in 1,2-dichloroethane. Then 0.1 ml of an acetic acid solution (1 molar in 1, 2-dichloroethane) and 0.06 g of NaBH (OAc) 3 (0.3 mmol) are added and the reaction mixture is stirred for 5 to 15 hours at room temperature. After the reaction has ended, the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether / ethyl acetate (9: 1). The product thus obtained is heated to 50 ° C. in 4 ml of ethanol and 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution. The precipitate is filtered off, washed twice with 1 ml of ethanol and then dried. a. N-thiophene-3-ylmethyl-1-4-diamino-benzene hydrochloride Aldehyde used: thiophene-3-carbaldehyde Yield: 0.025 g (90% of theory) Mass spectrum: MH + 205 (100) b. N-furan-3-ylmethyl-1, 4-diamino-benzene hydrochloride Aldehyde used: furan-3-carbaldehyde Yield: 0.025 g (95% of theory) Mass spectrum: MH + 189 (100) c. N- (1 H-Imidazol-2-ylmethv0-1, 4-diamino-benzene hydrochloride. Aldehyde used: Imidazole-2-carbaldehyde

Ausbeute: 0,025g (83% der Theorie) Massenspketrum: MH+ 189(100) d. N-Thiophen-2-ylmethyl-1.4-diamino-benzol Hvdrochlorid Verwendete Aldehydderivat: Thiophen-2-carbaldehyd Ausbeute: 0,025g (90% der Theorie) Massenspketrum: MH+ 205(100) e. N-Thiazol-2-ylmethyl-1 ,4-diamino-benzol Hvdrochlorid Verwendete Aldehydderivat: Thiazol-2-carbaldehyd Ausbeute: 0,025g (79% der Theorie) Massenspketrum: MH+ 316(100) f. N-(5-Nitro-thiophen-2-ylmethv0-1 ,4-diamino-benzol Hvdrochlorid Verwendete Aldehydderivat: 5-Nitro-thiophen-2-carbaldehyd Ausbeute: 0,025g (77% der Theorie)Yield: 0.025 g (83% of theory) mass spectrum: MH + 189 (100) d. N-thiophene-2-ylmethyl-1,4-diamino-benzene hydrochloride Aldehyde derivative used: thiophene-2-carbaldehyde Yield: 0.025 g (90% of theory) Mass spectrum: MH + 205 (100) e. N-thiazol-2-ylmethyl-1, 4-diamino-benzene hydrochloride Aldehyde derivative used: thiazole-2-carbaldehyde Yield: 0.025 g (79% of theory) Mass spectrum: MH + 316 (100) f. N- (5-nitro-thiophene-2-ylmethv0-1, 4-diamino-benzene hydrochloride Aldehyde derivative used: 5-nitro-thiophene-2-carbaldehyde Yield: 0.025 g (77% of theory)

Massenspketrum: MH+ 250(60)Mass spectrum: MH + 250 (60)

Beispiele 2: Synthese von N1-Heteroarylmethyl-2-methyl-1.4- diaminobenzolen und N4-Heteroarylmethyl-2-methyl-1 ,4-diaminobenzolen 0,033 g (0,15 mmol) einer Mischung aus N-(4-Amino-2-methyl-phenyl)- carbaminsäure-tert-butylester und N-(4-Amino-3-methyl-phenyl)- carbaminsäure-tert-butylester und 0,10 mmol des entsprechenden Aldehyds werden in 1 ,2-Dichlorethan gelöst. Anschliessend werden 0,1 ml einer Essigsäurelösung (1 -molar in 1 ,2-Dichlorethan) und 0,06 g NaBH(OAc)3 (0,3 mmol) zugegeben und die Reaktionmischung wird 5 bis 15 Stunden bei Raumtemperatur gerührt. Nach Beendigung der Reaktion wird die Reaktionsmischung in 10 ml Essigsäureethylester gegossen, die organische Phase mit Natriumhydrogencarbonat extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/ Essigsäureethylester (9:1) gereinigt. Das so erhaltene Produkt wird in 4 ml Ethanol und 1 ,5 ml einer 2,9-molaren ethanolische Salzsäurelösung auf 50 °C erwärmt.Examples 2: Synthesis of N1-heteroarylmethyl-2-methyl-1,4-diaminobenzenes and N4-heteroarylmethyl-2-methyl-1,4-diaminobenzenes 0.033 g (0.15 mmol) of a mixture of N- (4-amino-2- methyl-phenyl) -carbamic acid tert-butyl ester and N- (4-amino-3-methyl-phenyl) -carbamic acid tert-butyl ester and 0.10 mmol of the corresponding aldehyde are dissolved in 1, 2-dichloroethane. Then 0.1 ml of an acetic acid solution (1 molar in 1, 2-dichloroethane) and 0.06 g of NaBH (OAc) 3 (0.3 mmol) are added and the reaction mixture is stirred for 5 to 15 hours at room temperature. After the reaction has ended, the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether / ethyl acetate (9: 1). The product thus obtained is in 4 ml Ethanol and 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution heated to 50 ° C.

Der Niederschlag wird abfiltriert, zweimal mit 1 ml Ethanol gewaschen und sodann getrocknet. a. N1-(1 H-lmidazol-2-ylmethyl)-1.4-diamino-2-methyl-benzol Hvdrochlorid und N4-C1 H-lmidazol-2-ylmethyl)-1 ,4-diamino-2-methyl-benzol HvdrochloridThe precipitate is filtered off, washed twice with 1 ml of ethanol and then dried. a. N1- (1 H-imidazol-2-ylmethyl) -1,4-diamino-2-methyl-benzene hydrochloride and N4-C1 H-imidazol-2-ylmethyl) -1, 4-diamino-2-methyl-benzene hydrochloride

Verwendeter Aldehyd: lmidazol-2-carbaldehyd Ausbeute: 0,025g (40% der Theorie) Massenspketrum: MH+ 203(100) b. N1-Furan-3-ylmethyl-1.4-diamino-2-methyl-benzol Hvdrochlorid und N4-Furan-3-ylmethyl-1 ,4-diamino-2-methyl-benzol Hvdrochlorid Verwendete Aldehydderivat: Furan-3-carbaldehydAldehyde used: imidazole-2-carbaldehyde Yield: 0.025 g (40% of theory) Mass spectrum: MH + 203 (100) b. N1-furan-3-ylmethyl-1.4-diamino-2-methyl-benzene hydrochloride and N4-furan-3-ylmethyl-1, 4-diamino-2-methyl-benzene hydrochloride Aldehyde derivative used: furan-3-carbaldehyde

Ausbeute: 0,025g (45% der Theorie) Massenspketrum: MH+ 203(100) c. N1-Thiophen-2-ylmethyl-1.4-diamino-2-methyl-benzol Hvdrochlorid und N4-Thiophen-2-ylmethyl-1.4-diamino-2-methyl-benzol Hvdrochlorid Verwendete Aldehydderivat: Thiophen-2-carbaldehydYield: 0.025 g (45% of theory) mass spectrum: MH + 203 (100) c. N1-thiophene-2-ylmethyl-1.4-diamino-2-methyl-benzene hydrochloride and N4-thiophene-2-ylmethyl-1.4-diamino-2-methyl-benzene hydrochloride Aldehyde derivative used: thiophene-2-carbaldehyde

Ausbeute: 0,025g (42% der Theorie) Massenspketrum: MH+ 219(100)Yield: 0.025 g (42% of theory) mass spectrum: MH + 219 (100)

Beispiele 3: Synthese von N1-Heteroarylmethyl-2-(2'-hvdroxyethv0-1 ,4- diaminobenzolen und N4-Heteroarylmethyl-2-(2'-hvdroxyethyl)-1 ,4- diaminobenzolenExamples 3: Synthesis of N1-heteroarylmethyl-2- (2'-hvdroxyethv0-1, 4-diaminobenzenes and N4-heteroarylmethyl-2- (2'-hvdroxyethyl) -1, 4-diaminobenzenes

0,038 g (0,15 mmol) eine Mischung von N-(4-Amino-2-(2-hydroxyethyl)- phenyl)-carbaminsäure-tert-butylester und von N-(4-Amino-3-(2-hydroxy- ethyl)-phenyl)-carbaminsäure-tert-butylester und 0,10 mmol des entsprechenden Aldehyds werden in 1 ,2-Dichlorethan gelöst. Anschliessend werden 0,1 ml einer Essigsäurelösung (1-molar in 1 ,2-Dichlorethan) und 0,06 g NaBH(OAc)3 (0,3 mmol) zugegeben und die Reaktionmischung wird 5 bis 15 Stunden bei Raumtemperatur gerührt. Nach Beendigung der Reaktion wird die Reaktionsmischung in 10 ml Essigsäureethylester gegossen, die organische Phase mit Natrium- hydrogencarbonat extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/Essigsäureethylester (9:1) gereinigt. Das so erhaltene Produkt wird in 4 ml Ethanol und 1 ,5 ml einer 2,9-molaren ethanolische Salzsäurelösung auf 50 °C erwärmt. Der Niederschlag wird abfiltriert, zweimal mit 1 ml Ethanol gewaschen und sodann getrocknet. a. 2-{5-Amino-2-f(thiophen-3-ylmethyl)-amino1-phenyl)-ethanol Hydrochlorid und 2-{6-Amino-3-f(thiophen-3-ylmethvπ-amino1-phenyl)- ethanol Hvdrochlorid0.038 g (0.15 mmol) of a mixture of N- (4-amino-2- (2-hydroxyethyl) phenyl) carbamic acid tert-butyl ester and of N- (4-amino-3- (2-hydroxy- ethyl) -phenyl) -carbamic acid tert-butyl ester and 0.10 mmol of the corresponding aldehydes are dissolved in 1,2-dichloroethane. Then 0.1 ml of an acetic acid solution (1 molar in 1, 2-dichloroethane) and 0.06 g of NaBH (OAc) 3 (0.3 mmol) are added and the reaction mixture is stirred for 5 to 15 hours at room temperature. After the reaction has ended, the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether / ethyl acetate (9: 1). The product obtained in this way is heated to 50 ° C. in 4 ml of ethanol and 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution. The precipitate is filtered off, washed twice with 1 ml of ethanol and then dried. a. 2- {5-Amino-2-f (thiophene-3-ylmethyl) amino1-phenyl) ethanol hydrochloride and 2- {6-amino-3-f (thiophene-3-ylmethvπ-amino1-phenyl) ethanol hydrochloride

Verwendete Aldehydderivat: Thiophen-3-carbaldehyd Ausbeute: 0,025g (38% der Theorie) Massenspketrum: MH+ 249(15), [M-Thienyl]+ 152(100) b. 2-(5-Amino-2-f(thiophen-2-ylmethyl)-amino1-phenyll-ethanol Hvdrochlorid und 2-(6-Amino-3-r(thiophen-2-ylmethyl.-amino.-pheny.)- ethanol HvdrochloridAldehyde derivative used: thiophene-3-carbaldehyde Yield: 0.025 g (38% of theory) Mass spectrum: MH + 249 (15), [M-thienyl] + 152 (100) b. 2- (5-Amino-2-f (thiophene-2-ylmethyl) amino1-phenylethanol hydrochloride and 2- (6-amino-3-r (thiophene-2-ylmethyl.-amino.-pheny.) - ethanol hydrochloride

Verwendete Aldehydderivat: Thiophen-2-carbaldehydAldehyde derivative used: thiophene-2-carbaldehyde

Ausbeute: 0,025g (38% der Theorie)Yield: 0.025 g (38% of theory)

Massenspketrum: MH+ 249(15) , [M-Thienyl]+ 152(100) Beispiele 4 bis 16: HaarfärbemittelMass spectrum: MH + 249 (15), [M-Thienyl] + 152 (100) Examples 4 to 16: Hair Colorants

Es werden Haarfärbelösungen der folgenden Zusammensetzung hergestellt:Hair dye solutions of the following composition are produced:

1 ,25 mmol Entwicklersubstanz der Formel (I) gemäss Tabelle 11.25 mmol of developer substance of the formula (I) according to Table 1

1 ,25 mmol Kupplersubstanz gemäß Tabelle 11.25 mmol coupler substance according to Table 1

1 ,0 g Kaliumoleat (8-prozentige wässrige Lösung)1.0 g potassium oleate (8% aqueous solution)

1 ,0 g Ammoniak (22-prozentige wässrige Lösung)1.0 g ammonia (22% aqueous solution)

1 ,0 g Ethanol1.0 g of ethanol

0,3 g Ascorbinsäure ad 100,0 g Wasser0.3 g ascorbic acid ad 100.0 g water

50 g der vorstehenden Färbelösung werden unmittelbar vor der Anwendung mit 50 g einer 6-prozentigen wässrigen Wasserstoffperoxid- lösung vermischt. Anschliessend wird das Gemisch auf gebleichte Haare aufgetragen. Nach einer Einwirkungszeit von 30 Minuten bei 40 °C wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die resultierenden Färbungen sind in Tabelle 1 zusammengefaßt. 50 g of the above coloring solution are mixed with 50 g of a 6 percent aqueous hydrogen peroxide solution immediately before use. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 ° C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colorations are summarized in Table 1.

Figure imgf000020_0001
Tabelle 1 (Fortsetzung)
Figure imgf000020_0001
Table 1 (continued)

Figure imgf000021_0001
Beispiele 16 bis 56: Haarfärbemittel
Figure imgf000021_0001
Examples 16 to 56: Hair dye

Es werden Haarfärbelösungen der folgenden Zusammensetzung hergestellt:Hair dye solutions of the following composition are produced:

X g N-Heteroarylmethyl-p-phenylendiamin der Formel (I)X g N-heteroarylmethyl-p-phenylenediamine of the formula (I)

(Entwicklersubstanz E1 bis E4 gemäß Tabelle 2)(Developer substance E1 to E4 according to Table 2)

U g Entwicklersubstanz E8 bis E15 gemäß Tabelle 2U g of developer substance E8 to E15 according to Table 2

Y g Kupplersubstanz K11 bis K36 gemäß Tabelle 4Y g coupler substance K11 to K36 according to Table 4

Z g direktziehender Farbstoff D1 bis D3 gemäß Tabelle 3Z g direct dye D1 to D3 according to Table 3

10,000 g Kaliumoleat (8-prozentige wässrige Lösung)10,000 g potassium oleate (8% aqueous solution)

10,000 g Ammoniak (22-prozentige wässrige Lösung)10,000 g ammonia (22 percent aqueous solution)

10,000 g Ethanol10,000 g ethanol

0,300 g Ascorbinsäure ad 100,000 g Wasser0.300 g of ascorbic acid to 100,000 g of water

30 g der vorstehenden Färbelösung werden unmittelbar vor der Anwendung mit 30 g einer 6-prozentigen wässsrigen Wasserstoffperoxidlösung vermischt. Anschliessend wird das Gemisch auf gebleichte Haare aufgetragen. Nach einer Einwirkungszeit von 30 Minuten bei 40 "Celsius wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die Färbeergebnisse sind in Tabelle 5 zusammengefasst. 30 g of the above coloring solution are mixed with 30 g of a 6% aqueous hydrogen peroxide solution immediately before use. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 5.

Beispiele 57 bis 80: HaarfärbemittelExamples 57 to 80: hair dye

Es werden cremeförmige Farbträgermassen der folgenden Zusammensetzung hergestellt:Cream-like color carrier compositions of the following composition are produced:

X g N-Heteroarylmethyl-p-phenylendiamin der Formel (I)X g N-heteroarylmethyl-p-phenylenediamine of the formula (I)

(Entwicklersubstanz E1 bis E4 gemäß Tabelle 2) U g Entwicklersubstanz E8 bis E15 gemäß Tabelle 2 Y g Kupplersubstanz K11 bis K36 gemäss Tabelle 4 Z g direktziehender Farbstoff D2 gemäss Tabelle 3 15,0 g Cetylalkohol 0,3 g Ascorbinsäure 3,5 g Natriumlaurylalkoholdiglycolethersulfat, 28-prozentige wässrige Lösung 3,0 g Ammoniak, 22-prozentige wässrige Lösung 0,3 g Natriumsulfit, wasserfrei ad 100,0 g Wasser(Developer substance E1 to E4 according to Table 2) U g developer substance E8 to E15 according to Table 2 Y g coupler substance K11 to K36 according to Table 4 Z g direct dye D2 according to Table 3 15.0 g cetyl alcohol 0.3 g ascorbic acid 3.5 g sodium lauryl alcohol diglycol ether sulfate , 28 percent aqueous solution 3.0 g ammonia, 22 percent aqueous solution 0.3 g sodium sulfite, anhydrous ad 100.0 g water

30 g der vorstehenden Färbecreme werden unmittelbar vor der Anwendung mit 30 g einer 6-prozentigen Wasserstoffperoxidlösung vermischt. Anschliessend wird das Gemisch auf das Haar aufgetragen. Nach einer Einwirkzeit von 30 Minuten wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die Färbeergebnisse sind in Tabelle 6 zusammengefasst. 30 g of the above coloring cream are mixed with 30 g of a 6 percent hydrogen peroxide solution immediately before use. The mixture is then applied to the hair. After a contact time of 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The staining results are summarized in Table 6.

Figure imgf000024_0001
Figure imgf000024_0001

Tabelle 3:Table 3:

Figure imgf000024_0002
Figure imgf000025_0001
Tabelle 5: Haarfärbemittel
Figure imgf000024_0002
Figure imgf000025_0001
Table 5: Hair dye

Figure imgf000026_0001
Figure imgf000026_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000027_0001
Figure imgf000027_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000028_0001
Figure imgf000028_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000029_0001
Figure imgf000029_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000030_0001
Figure imgf000030_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000031_0001
Figure imgf000031_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000032_0001
Figure imgf000032_0001

Tabelle 5 (Fortsetzung)Table 5 (continued)

Figure imgf000033_0001
Figure imgf000033_0001

Tabelle 6: HaarfärbemittelTable 6: Hair dye

Figure imgf000034_0001
Figure imgf000034_0001

Tabelle 6: (Forsetzung)Table 6: (continued)

Figure imgf000034_0002
Tabelle 6: (Forsetzung)
Figure imgf000034_0002
Table 6: (continued)

Figure imgf000035_0001
Figure imgf000035_0001

Tabelle 6: (Forsetzung)Table 6: (continued)

Figure imgf000035_0002
Figure imgf000035_0002

Alle Prozentangaben stellen, soweit nicht anders angegeben, Gewichtsprozente dar. Unless otherwise stated, all percentages are percentages by weight.

Claims

P a t e n t a n s p r ü c h e Patent claims 1. N-Heteroarylmethyl-p-phenylendiamin-Derivate der allgemeinen Formel (I) oder deren physiologisch verträgliche, wasserlösliche Salze,1. N-heteroarylmethyl-p-phenylenediamine derivatives of the general formula (I) or their physiologically compatible, water-soluble salts,
Figure imgf000036_0001
worin
Figure imgf000036_0001
wherein X1 gleich Schwefel, Stickstoff, C-R6 oder N-R5 ist;X1 is sulfur, nitrogen, C-R6 or N-R5; X2 gleich Schwefel, Stickstoff, C-R6 oder N-R5 istX2 is sulfur, nitrogen, C-R6 or N-R5 X3 gleich Schwefel, Stickstoff, Sauerstoff, C-R6 oderX3 is sulfur, nitrogen, oxygen, C-R6 or N-R5 ist;Is N-R5; R1 gleich Wasserstoff, einer CrC4-Alkylgruppe oder einerR1 is hydrogen, a CrC 4 alkyl group or one CrC4-Hydroxyalkylgruppe ist ;Is CrC 4 hydroxyalkyl group; R2,R3 gleich oder verschieden sein können und unabhängig voneinander gleich Wasserstoff oder einer Ci-Cβ- Alkylgruppe sind;R2, R3 may be the same or different and, independently of one another, are hydrogen or a Ci-Cβ-alkyl group; R4,R6 gleich oder verschieden sein können und unabhängig voneinander gleich Wasserstoff, einem Halogenatom, einer Cyanogruppe, einer C-ι-C4-Alkoxygruppe, einer CrC6-Alkylgruppe, einer CrC4-Alkylthioethergruppe, einer Mercaptogruppe, einer Nitrogruppe, einer Aminogruppe, einer Cι-C4-Alkylaminogruppe, einer Di(Cι-C4)-alkylaminogruppe, einer Di(CrC4-hydroxy- alkyl)aminogruppe, einer Cι-C4-Hydroxyalkylamino- gruppe, einer Trifluormethangruppe, einer -C(O)CH3- Gruppe, einer -C(O)CF3-Gruppe, einer -Si(CH3)3- Gruppe, einer Cι-C4-Hydroxyalkylgruppe oder einer C3-C4 Dihydroxyalkylgruppe sind;R4, R6 can be the same or different and, independently of one another, the same hydrogen, a halogen atom, a cyano group, a C 1 -C 4 alkoxy group, a CrC 6 alkyl group, a CrC 4 alkyl thioether group, a mercapto group, a nitro group, an amino group , a C 1 -C 4 -alkylamino group, a di (C 1 -C 4 ) -alkylamino group, a di (CrC 4 -hydroxy- alkyl) amino group, a C 1 -C 4 -hydroxyalkylamino group, a trifluoromethane group, a -C (O) CH 3 group, a -C (O) CF 3 group, an -Si (CH 3 ) 3 group, a Cι-C 4 hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl; R5 gleich Wasserstoff, einer CrCβ-Alkylgruppe, einerR5 is hydrogen, a CrCβ alkyl group, one Cι-C4-Hydroxyalkylgruppe, einer Phenylgruppe oder einer Acetylgruppe ist; wobei mindestens einer und maximal zwei der Reste X1 bis X3 gleichC 1 -C 4 hydroxyalkyl group, a phenyl group or an acetyl group; where at least one and a maximum of two of the radicals X1 to X3 are the same C-R6 sind und maximal einer der Reste X1 bis X3 gleich Schwefel,C-R6 and a maximum of one of the radicals X1 to X3 are sulfur, Sauerstoff oder N-R5 ist.Is oxygen or N-R5. 2. N-Heteroarylmethyl-p-phenylendiamin-Derivat gemäß Anspruch 1 , dadurch gekennzeichnet, dass (i) R1, R2 und R3 oder R1, R2, R3 und R4 Wasserstoff bedeuten oder (ii) R1, R2 und R3 oder R1, R2, R3 und R4 Wasserstoff bedeuten und X1 gleich Schwefel oder N-H ist und X2 gleich Stickstoff oder C-R6 ist und X3 gleich C-R6 ist oder (iii) R1, R2 und R3 oder R1, R2, R3 und R4 gleich Wasserstoff sind und X3 gleich Schwefel oder Sauerstoff ist und X1 und X2 gleich C-R6 sind oder (iv) R1, R2 und R3 oder R1, R2, R3 und R4 gleich Wasserstoff sind und X2 gleich Schwefel oder Sauerstoff ist und X1 und X3 gleich C-R6 sind.2. N-heteroarylmethyl-p-phenylenediamine derivative according to claim 1, characterized in that (i) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen or (ii) R1, R2 and R3 or R1, R2 , R3 and R4 are hydrogen and X1 is sulfur or NH and X2 is nitrogen or C-R6 and X3 is C-R6 or (iii) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X3 is sulfur or oxygen and X1 and X2 are C-R6 or (iv) R1, R2 and R3 or R1, R2, R3 and R4 are hydrogen and X2 is sulfur or oxygen and X1 and X3 are C-R6 are. 3. N-Heteroarylmethyl-p-phenylendiamin-Derivat gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das N-Heteroarylmethyl-p- phenylendiamin-Derivat der Formel (I) ausgewählt ist aus N-Thiophen-3- ylmethyl-1 ,4-diamino-benzol, N-Furan-3-ylmethyl-1 ,4-diamino-benzol, N-(1 H-lmidazol-2-ylmethyl)-1 ,4-diamino-benzol, N-(1 H-Pyrrol-2-ylmethyl)- 1 ,4-diamino-benzol und N-Thiophen-2-ylmethyl-1 ,4-diamino-benzol oder deren physiologisch verträglichen Salzen. 3. N-heteroarylmethyl-p-phenylenediamine derivative according to claim 1 or 2, characterized in that the N-heteroarylmethyl-p-phenylenediamine derivative of the formula (I) is selected from N-thiophene-3-ylmethyl-1,4 -diamino-benzene, N-furan-3-ylmethyl-1, 4-diamino-benzene, N- (1 H-imidazol-2-ylmethyl) -1, 4-diamino-benzene, N- (1 H-pyrrole- 2-ylmethyl) - 1, 4-diamino-benzene and N-thiophene-2-ylmethyl-1, 4-diamino-benzene or their physiologically tolerable salts. 4. Mittel zum oxidativen Färben von Keratinfasem auf der Basis einer Entwicklersubstanz-Kupplersubstanz-Kombination, dadurch gekennzeichnet, dass es als Entwicklersubstanz mindestens ein N-Heteroaryl- methyl-p-phenylendiamin-Derivat der Formel (I) nach einem der Ansprüche 1 bis 3 enthält.4. Agent for the oxidative dyeing of keratin fibers based on a developer substance-coupler substance combination, characterized in that it contains at least one N-heteroaryl-methyl-p-phenylenediamine derivative of the formula (I) as a developer substance according to one of claims 1 to 3 contains. 5. Mittel nach Anspruch 4, dadurch gekennzeichnet, dass es die Verbindung der Formel (I) in einer Menge von 0,005 bis 20 Gewichtsprozent enthält.5. Composition according to claim 4, characterized in that it contains the compound of formula (I) in an amount of 0.005 to 20 weight percent. 6. Mittel nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass die Kupplersubstanz ausgewählt ist aus der Gruppe bestehend aus 2,6-Diamino-pyridin, 2-Amino-4-[(2-hydroxyethyl)amino]-anisol, 2,4-Diamino-1 -fluor-5-methyl-benzol, 2,4-Diamino-1 -methoxy-5-methyl- benzol, 2,4-Diamino-1-ethoxy-5-methyl-benzol, 2,4-Diamino-1-(2- hydroxyethoxy)-5-methyl-benzol, 2,4-Di[(2-hydroxyethyl)amino]-1 ,5- dimethoxy-benzol, 2,3-Diamino-6-methoxy-pyridin, 3-Amino-6-methoxy-2- (methylamino)-pyridin, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino- 2,6-dimethoxy-pyridin, 1 ,3-Diamino-benzol, 2,4-Diamino-1-(2-hydroxy- ethoxy)-benzol, 2,4-Diamino-1 ,5-di(2-hydroxyethoxy)-benzol, 1-(2-Amino- ethoxy)-2,4-diamino-benzol, 2-Amino-1-(2-hydroxyethoxy)-4-methylamino- benzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxyethyl)amino]- anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1 -ethoxy-benzol, 5-Methyl-2- (1 -methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Amino- ethyl)amino]-anilin, 1 ,3-Di(2,4-diaminophenoxy)-propan, Di(2,4-diamino- phenoxy)-methan, 1 ,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2-hydroxy- ethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethyl- amino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl- phenol, 5-Amino-4-methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl- phenol, 3-Amino-2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino- 2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-2- methyl-phenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-Methoxyethyl)- aminoj-phenol, 5-Amino-2-ethyl-phenol, 2-(4-Amino-2-hydroxyphenoxy)- ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxy- propyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-2-methyl- phenol, 2-Amino-3-hydroxy-pyridin, 5-Amino-4-chlor-2-methyl-phenol, 1-Naphthol, 1 ,5-Dihydroxy-naphthalin, 1 ,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol- acetat, 1 ,3-Dihydroxy-benzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1,3- dihydroxy-benzol, 1 ,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1 ,5-Dichlor- 2,4-dihydroxy-benzol, 1 ,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy- phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1 ,3-benzo- dioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino- benzoesäure, 3,4-Dihydro-6-hydroxy-1 ,4(2H)-benzoxazin, 6-Amino-3,4- dihydro-1 ,4(2H)-benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy- indol, 7-Hydroxy-indol und 2,3-lndolindion.6. Composition according to claim 4 or 5, characterized in that the coupler substance is selected from the group consisting of 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2.4 -Diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino -1- (2-hydroxyethoxy) -5-methyl-benzene, 2,4-di [(2-hydroxyethyl) amino] -1, 5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3 -Amino-6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diamino-benzene , 2,4-diamino-1- (2-hydroxyethoxy) benzene, 2,4-diamino-1, 5-di (2-hydroxyethoxy) benzene, 1- (2-aminoethoxy) -2, 4-diamino-benzene, 2-amino-1- (2-hydroxyethoxy) -4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3- [di (2-hydroxyethyl) amino] aniline, 4-amino- 2-di [(2-hydroxyethyl) amino] -1-ethoxybenzene, 5-methyl-2- (1-methylethyl) phenol, 3 - [(2-hydroxyethyl) amino] aniline, 3 - [(2nd -Amino-ethyl) amino] -aniline, 1, 3-di (2,4-dia minophenoxy) propane, di (2,4-diaminophenoxy) methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis (2-hydroxyethyl) aminotoluene, 4- Hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methyl- phenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4- dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2 - [(3-hydroxyphenyl) amino] acetamide, 5- [ (2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] phenol, 3 - [(2-methoxyethyl) aminoj-phenol, 5-amino-2-ethylphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 3 - [(2,3-dihydroxypropyl) amino] -2-methyl- phenol, 3 - [(2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3-hydroxy-pyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1, 5 -Dihydroxy-naphthalene, 1, 7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1, 3-dihydroxy-benzene, 1-chlorine -2,4-dihydroxy-benzene, 2-chloro-1,3-dihydroxy-benzene, 1, 2-dichloro-3,5-dihydroxy-4-methyl-benzene, 1, 5-dichloro-2,4-dihydroxy -benzene, 1, 3-dihydroxy-2-methyl-benzene, 3,4-methylenedioxy-phenol, 3,4-methy lendioxy-aniline, 5 - [(2-hydroxyethyl) amino] -1, 3-benzo-dioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3,4 -Dihydro-6-hydroxy-1, 4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1, 4 (2H) -benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6 -Dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and 2,3-indole-indione. 7. Mittel nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die Entwicklersubstanzen und Kupplersubstanzen, bezogen auf die Gesamtmenge des Färbemittels, jeweils in einer Gesamtmenge von 0,005 bis 20 Gewichtsprozent enthalten sind.7. Composition according to one of claims 4 to 6, characterized in that the developer substances and coupler substances, based on the total amount of the colorant, are each present in a total amount of 0.005 to 20 percent by weight. 8. Mittel nach einem der Ansprüche 4 bis 7 , dadurch gekennzeichnet, dass es zusätzlich mindestens einen direktziehenden Farbstoff enthält. 8. Agent according to one of claims 4 to 7, characterized in that it additionally contains at least one substantive dye. 9. Mittel nach einem der Ansprüche 4 bis 8, dadurch gekennzeichnet, dass es ein Haarfärbemittel ist. 9. Composition according to one of claims 4 to 8, characterized in that it is a hair dye.
PCT/EP2001/002840 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents Ceased WO2002018365A1 (en)

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CA002435328A CA2435328C (en) 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phenylenediamine derivatives as well as oxidation dyeing agents containing these compounds
EP01925442A EP1313724B1 (en) 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents
AU2001252194A AU2001252194B2 (en) 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents
DE50102156T DE50102156D1 (en) 2000-08-31 2001-03-14 N-HETEROARYLMETHYL-P-PHENYLENE DIAMINE DERIVATIVES AND OXIDATION COLOR CONTAINING THESE COMPOUNDS
AU5219401A AU5219401A (en) 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phenylendiamine derivatives and compounds containing oxidation colouring agents
BR0107155-6A BR0107155A (en) 2000-08-31 2001-03-14 Derivatives of n-heteroarylmethyl-p-phenylenediamine as well as oxidation dyeing agents containing these compounds
JP2002523483A JP2004507532A (en) 2000-08-31 2001-03-14 N-Heteroarylmethyl-p-phenylenediamine derivatives and oxidation dyes containing this compound
US10/111,464 US6849097B2 (en) 2000-08-31 2001-03-14 N-heteroarylmethyl-p-phnylendiamine derivatives and compounds containing oxidationcoloring agents
AT01925442T ATE265446T1 (en) 2000-08-31 2001-03-14 N-HETEROARYLMETHYL-P-PHENYLENEDIAMINE DERIVATIVES AND OXIDATION DYES CONTAINING THESE COMPOUNDS
US10/922,443 US6887281B2 (en) 2000-08-31 2004-08-20 N-heteroarylmethyl-p-phenylenediamine derivatives as well as oxidation dyeing agents containing these compounds

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DE10152941A1 (en) * 2001-10-26 2003-05-08 Henkel Kgaa New developer components
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US5183941A (en) * 1989-05-18 1993-02-02 Clairol Incorporated Hair dye coupler compounds
US5540738A (en) * 1991-11-26 1996-07-30 Chan; Alexander C. Oxidative hair coloring composition and process for dyeing human keratinous fibers
EP0984007A1 (en) * 1998-09-02 2000-03-08 L'oreal Cationic orthophenylenediamines, their use for the oxidation dyeing of keratinous fibres, dyeing compositions and dyeing methods
US6042620A (en) * 1998-03-19 2000-03-28 Wella Ag p-diaminobenzene derivative compounds and dye compositions containing same

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DE4110995A1 (en) * 1991-04-05 1992-10-08 Henkel Kgaa HAIR DRYER WITH DIRECT DYES
US5540738A (en) * 1991-11-26 1996-07-30 Chan; Alexander C. Oxidative hair coloring composition and process for dyeing human keratinous fibers
US6042620A (en) * 1998-03-19 2000-03-28 Wella Ag p-diaminobenzene derivative compounds and dye compositions containing same
EP0984007A1 (en) * 1998-09-02 2000-03-08 L'oreal Cationic orthophenylenediamines, their use for the oxidation dyeing of keratinous fibres, dyeing compositions and dyeing methods

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